Substituted phenylurea herbicides

ABSTRACT

THE INVENTION IS DIRECTED TO HERBICIDALLY ACTIVE COMPOUNDS AND COMPOSITIONS AND TO HERBICIDAL PROCESSES HAVING AS AN ACTIVE INGREDIENT A COMPOUND REPRESENTED BY THE FORMULA:   (((Z)N-PHENYL)-CH(-R&#34;&#34;)-Y-),(R&#39;&#39;-N(-R&#34;)-CO-NH-),W-BENZENE   WHEREIN R&#39;&#39; IS SELECTED FROM THE GROUP CONSISTING OF H, CH3, C2H5; R&#34; IS A MEMBER SELECTED FROM THE GROUP CONSISTING OF H, AND LOWER ALKYL; W IS A MEMBER SELECTED FROM THE GROUP CONSISTING OF H, HALO, LOWER ALKYL, AND NO2; Y IS A MEMBER SELECTED FROM THE GROUP CONSISTING OF S, O, SO, AND SO2; Z IS A MEMBER SELECTED FROM THE GROUP CONSISTING OF NO2, NH2, N(R&#34;&#39;&#39;)2, HALO, LOWER ALKYL, XM-R&#34;&#39;&#39;-, R&#34;&#39;&#39;O-, R&#34;&#39;&#39;S(O)N-, R&#34;&#39;&#39;NH-, -OH, -COOH, -COOR&#34;&#39;&#39;, -CN, -NHCON(R&#34;&#39;&#39;)2 AND R&#34;&#39;&#39;CONH-; X IS HALO; R&#34;&#39;&#39; IS LOWER ALKYL; R&#34;&#34; IS HYDROGEN, LOWER ALKYL OR PHENYL; N IS 0, 1 TO 2; AND M IS 1, 2 OR 3.

United States Patent (lflice 3,819,697 SUBSTITUTED PHENYLUREA HERBICIDES Barrington Cross, Rocky Hill, N.J., assignor to American Cyanamid Company, Stamford, Conn. No Drawing. Filed Mar. 4, 1970, Ser. No. 16,580 Int. Cl. C07c 127/18 US. Cl. 260-553 A 5 Claims ABSTRACT OF THE DISCLOSURE The invention is directed to herbicidally active compounds and compositions and to herbicidal processes having as an active ingredient a compound represented by the formula:

wherein R is selected from the group consisting of H, CH C H R is a member selected from the group consisting of H, and lower alkyl; W is a member selected from the group consisting of H, halo, lower alkyl, and N Y is a member selected from the group consisting of S, 0, SO, and S0 Z is a member selected from the group consisting of N0 NH N(R') halo, lower alkyl, X R, R"'O, R"'S(O) R"NH, OH, -CO0H, COOR'", -CN, NHCON(R") and RCONH; X is halo; R is lower alkyl; R"" is hydrogen, lower alkyl or phenyl; n is 0, 1 to 2; and m is 1, 2 or 3.

NHCONR'R" Formula I wherein R is selected from the group consisting of H, CH C H R" is a member selected from the group consisting of H, and lower alkyl; W is a member selected from the group consisting of H, halo, lower alkyl, and N0 Y is a member selected from the group consisting of S, 0, SO, and S0 Z is a member selected from the group consisting of N0 NH N(R") halo, lower alkyl, X R"--, RO-, R"S(O R"'NH--, OH, COOH, COOR, --CN, NHCON(R') and R"'CONH; X is halo; R is lower alkyl; R is hydrogen, lower alkyl or phenyl; n is 0, 1 or 2; and m is 1, 2,or 3. As used herein, halo is a member selected from the group consisting of fluoro, bromo, chloro and iodo; lower alkyl has from 1 to 4 carbon atoms, such as, for example, methyl, ethyl, n-propyl, iswpropyl, n-butyl and t-butyl.

It has now been found that unexpectedly effective control of undesirable plant life can be attained by application of the compounds of Formula I. The compounds may be advantageously employed in standard preemergence or postemergence treatment of undesired plant life. For example, they are herbicidally effective when applied to the foliage of either monocotyledonous or dicotyledonous plants or when applied to soils or sand containing seeds of such plants.

In general, the compounds of Formula I may be conveniently prepared by reacting the appropriately substi- Patented June25, 1974 tuted aniline precursors with a variety of reactants such as (1) an appropriately substituted carbamoyl chloride, (2) phosgene and then an appropriate primary and secondary amine or (3) an appropriate alkyl isocyanate. General procedures are set forth below:

Carbamoyl Chloride Synthesis of the Phenylureas wherein R, R", W, Y, Z and n are as previously defined.

A substitued aniline compound of Formula II (0.1 mole) and 0.1 mole of an acid acceptor such as triethylamine, pyridine or sodium carbonate are added to an aprotic solvent such as benzene, a liquid hydrocarbon, acetone, ether, dioxane, dimethylformamide, acetonitrile, tetrahydrofuran, or the like, and then treated with approximately 0.1 to 0.5 moles of the appropriately substituted carbamoyl chloride. The reaction is generally carried out at a temperature of about 10 C. with stirring. The reaction is usually complete in 30 minutes at room temperature, however, sometimes warming to solvent reflux is required. When using dimethylformamide or acetone as the solvent, the product is isolated by pouring into ice water, making it alkaline with sodium acetate and filtering off the crude product. Purification may be accomplished by recrystallization or by chromatographic separation on a column of silica gel using an acetone-benzene mixture as the eluent. When using a solvent which is nonmiscible with water, e.g., benzene or ethers, the reaction is quenched by successively washing the organic layer with: (1) dilute aqueous, hydrochloric acid, (2) water, (3) dilute, aqueous sodium carbonate. The organic layer is then dried over anhydrous magnesium sulfate and the solvent is removed by distillation. The crude urea compound is purified as set forth above.

Phosgene Synthesis of the Phenylureas C0 C12 CHRIVIIY W The substituted aniline compound of Formula II (0.1 mole) is dissolved in a suitable aprotic solvent, such as, for example, toluene (100-500 ml.) optionally containing a base, such as, sodium acetate or sodium carbonate (0.2 mole). Phosgene is bubbled through the solution, effecting a temperature rise to from about 50 to about C. After 1 hour, the mixture is filtered and evaporated under reduced pressure. The residue is dissolved in toluene (50500 ml.) and gaseous dimethylamine is added at 15 with ice cooling. The alkaline solution is ether extracted, washed with dilute hydrochloric acid, and then water. Insoluble impurities are filtered off. The ether solution is dried over anhydrous magnesium sulfate and then evaporated to dryness. The residue is purified by recrystallization.

Alkyl Isocyanate Synthesis of the Phenylureas A substituted aniline compound of Formula II (0.01 mole) is dissolved in from about 20 to about 100 ml. of a suitable aprotic solvent, such as, for example, ethyl ether, benzene, toluene, xylene, acetone, dimethylformamide, light petroleum, dioxane or tetrahydrofuran. One drop of triethylamine or pyridine is added and then the solution is cooled to about C. on an ice bath. The appropriately substiuted alkyl isocyanate (preferably from about 0.01 to about 0.05 mole) is added to the solution with stirring and the resulting solution is allowed to sit overnight at room temperature. The desired urea in the form of a precipitate is removed by filtration and purified by recrystallization.

Where the desired product is not formed upon standing overnight, the reaction mixture is heated to 100 C. for a period of about 120 hours. Where it does not precipitate from solution, precipitation is induced by the addition of hexane to the reaction mixture.

Oxidation of Benzylthio Phenylureas Alternatively, the benzylsulfinyl and benzylsulfonyl phenylurea compounds of Formula I may be prepared by oxidation of the appropriate benzylthio phenylurea compound. A general procedure and the reaction scheme is as follows:

( )n III W )11 (O)n Oxidation of a benzylthio phenylurea compound of I Formula 111 to the corresponding sulfinyl or sulfonyl compound is accomplished by standard oxidation procedures. Illustrative procedures are oxidation with a peracid, such as peracetic acid, pertrifluoroacetic acid, or a perbenzoic acid; oxidation with hydrogen peroxide, or with potassium permanganate. A preferred oxidizing agent is m-chloroperbcnzoic acid in chloroform or suitable aprotic solvent, such as toluene or benzene.

Formation of the sulfonyl compound by oxidation may be effected by mixing the appropriate benzylthio phenylurea with 2 moles of an oxidizing agent, such as, mchloroperbenzoic acid in a chloroform solution at for a period of about 1 to about 40 hours. The desired product is isolated by washing with aqueous sodium carbonate, drying over an hydrous magnesium sulfate, evaporating off the solvent and purifying the resulting solid by recrystallization from a solvent, such as chloroform. The corresponding sulfinyl compounds are prepared by mixing the appropriate benzylthio phenylurea compound with one molar equivalent of m-chloroperbenzoic acid in a chloroform solution at 5 C. The desired product is generally isolated as above; however, in some cases, chromatography on a silica gel column with an ethyl acetate eluent was required in order to effect purification of the crystalline product.

Preparation of the Aniline Precursors III W (Z)n wherein W, Z, R" and n are as defined above, and V is oxygen or sulfur.

Synthesis of the Phenylureas by Nucleophilic Substitution Further synthetic routes to the benzyloxyphenylureas are provided by nucleophilic substitutions between a halobenzyl compound, such as, benzyl bromide or chloride and a nitrophenol or a hydroxy substituted phenylurea.

The benzylthiophenylureas may be prepared by either reacting a benzyl mercaptan with the appropriate bromo or chloro substituted nitrobenzene or by reacting a nitrophenyl mercaptan with a halobenzyl compound, such as, benzyl chloride or bromide.

In a typical nucleophilic substitution, equal molar quantities of a base, such as, anhydrous potassium carbonate, potassium t-butoxide, sodium methoxide or pyridine, the halo compound and the hydroxy or thiohydroxy compound are refluxed in acetone for a period of up to 8 hours or more. The resulting inorganic salts are dissolved by the addition of water. If the desired product precipitates from the aqueous solution, it is collected by filtration and dried. Where precipitation does not occur, the desired product is extracted from the aqueous solution with an organic solvent, such as, benzene, or chlorform; and, the resulting solution is dried over anhydrous magnesium sulfate and evaporated to dryness. The crystalline products are purified by recrystallization or by chromatography on a silica gel column.

Illustrative of suitable carbamoyl chlorides are dimethyl carbamoyl chloride, diethyl carbamoyl chloride, ethyl npropyl carbamoyl chloride, methyl t-butyl carbamoyl chloride, etc.

Illustrative of suitable alkyl isocyanate compounds are methyl isocyanate, ethyl isocyanate, n-propyl isocyanate, iso-propyl isocyanate, n-butyl isocyanate, t-butyl isocyanate, etc.

Illustrative of suitable amines used in the phosgene synthesis of the phenylureas are, for example, ammonia, methylamine, ethylamine, dimethylamine, diethylamine, methylethylarnine, i-propylamine, n-butylamine, t-butylamine, etc.

Illustrative of the numerous suitable substituted, aniline compounds of Formula II are, for example:

2 benzyloxy aniline,

3-(benzyloxy -4-chloroaniline,

3- (p-chlorobenzyloxy) aniline,

4- (benzyloxy -3-chloroaniline,

4- benzy'loxy -2-chloroaniline,

4 benzyloxy -3 -nitroaniline,

4- (p-chlorobenzyloxy -3-chloroaniline, 4- (m-bromobenzyloxy -2-bromoaniline, 3-chloro-4 (p-nitrobenzyloxy) aniline, 3-(p-nitrobenzyloxy) aniline, 4-(p-aminobenzyloxy -3-chloroaniline, 2-benzyloxy-4-iodoaniline,

3- 3-chloro-4- (benzylsulfonyl phenyl] l l-dimethylurea,

3-[p-(benzylthio)phenyl]-1,1-dimethylurea,

3-[p-(bcnzylsulfonyl)phenyl]-1,1-dimethylurea,

l- [p-( benzylsulfonyl) phenyl] -3-methylurea,

1- [P- -Chlorobenzyloxy phenyl] -3 -methylurea,

3-[m-(benzyloxy)phenyl]-1,1-dimethylurea,

1- mbenzyloxy phenyl] -3-methylurea,

3-[p-(benzyloxy)phenyl]-1,1-dimethylurea,

1- [p( benzylthio phenyl] -3-methylurea,

3-[3-chloro-4'(p-chloro'benzyloxy)phenyl]-l,l-dimethy1- urea,

3-[4 (benzyloxy)-3-chlorophenyl]=1,1-dimethylurea,

3-[p-(p-chlorobenzyloxy)phenyl]-1,1-dimethylurea,

1- 3-chloro-4- (p-chlorobenzyloxy phenyl -3-methylu re a,

3-[4-(p-chlorobenzyloxy)-3-nitrophenyl]-1,1-dimethylurea,

3-[4-(p-hydroxybenzyloxy)phenyl]-1,1-dimethylurea,

3-[3-(p-chlorobenzyloxy)phenyl]-1,1-diethyl urea,

1- [3-chloro-4- (p-carbethoxybenzyloxy phenyl] -3-diethylurea,

1- 3-n-propyl-4- ('benzyloxy phenyl -3-t-butylurea,

3- 3-(benzylthio -4-chlorophenyl] -1, l-dimethylurea,

3-[3-(benzylthio)-4-chlorophenyl]-urea,

3-[3-(p-chlorobenzylsulfonyl)phenyl]=1, l-dimethylurea,

3-[3-(p-chloro-a-methylbenzylsulfonyl)phenyl]-1,1-

dimethylurea,

1- [4-( benzylsulfinyl -3-chlorophenyl] -3-t butylurea,

1- [4- (Z-CthYlbCl'lZYlSUlfiHYl -3-chlorophenyl] -3-t-butylurea,

1- [4- (benzylthio -3-nitropehnyl -3-sec-butylurea,

1- [4- a-methylbenzylthio -3-nitropehnyl -3-sec-butylurea,

1- 4- (p-chlorobenzylsulfonyl-3-chlorophenyl] -3-t-butylurea,

1- [4- (p-chloro-a-n-butylbenzylsulfonyl-3-chlorophenyl] 3-t-butylurea,

3- [3-chloro-4-(p-nitrobenzylsulfinyl )phenyl]- 1, 1-

dimethylurea,

3-[4-(p-nitrobenzylthio)phenyl]-1,1-dimethylurea,

3-[4-(p-am'inobenzylsulfonyl) -3-chlorophenyl] -1,'l-dimethylurea,

3- [4- (p-am'inobenzylsulfinyl phenyl] 1 l-dimethylurea,

3- [3-chloro-4-(p-dimethylaminobenzylthio)phenyl]-1, 1-

dimethylurea,

3-[3-chloro-4-(p-methylbenzyloxy)phenyl]-1, l-dimethylurea,

3- [3-chloro-4- (p-ethylaminobenzylsulfonyl)phenyl]-1,1-

dimethylurca,

3- [4- (p-dimethylamino'benzylsulfinyl phenyl] l l-dimethylurea,

3- 3-chloro-4- (p-methylthiobenzylthio phenyl]-1,1-dimethylurea,

3-[4-(p-methylthiobenzylsulfonyl)phenyl]-1,1-dimethylurea,

3- 3-chloro-4- (p-methylsulfonylbenzylsulfinyl) phenyl] 1,1-dimethylurea,

3-[4-(p-methylsulfonylbenzylthio)phenyl]-1,1-dimethylurea,

3-{3-chloro-4- [p- 3,3-dimethylureido benzylsulfonyl] phenyl}-1,1-dimethylurea,

3- [4- (p-propionamidobenzylsulfinyl phenyl] 1 1-diethylurea,

3-[3-chloro-4-(p-methoxybenzylthio)phenyl]-1,1-dimethylurea,

3- [4- (p-bromobenzylsulfonyl phenyl] -1 l-dimethylu rea,

l- 2-methyl-4- benzylthio phenyl -3-t-butylurea,

3- [4- (p-methylbenzylsulfonyl phenyl] l,'1-dimethylurea,

3- 3-chloro-4- p-methylbenzylsulfinyl phenyl l-t-butyll-methylurea,

3-[4-(o-methylbenzylthio)phenyl]-1,l-dimethylurea,

3-[3-chloro-4-(o-methylbenzylsulfonyl)phenyl]-1,1-

dimethylurea,

3-[3-(p-cyanobenzylsulfinyl)phenyl]-1,1-dimethylurea,

1- 3-chloro-4- (p-methylbenzyloxy phenyl] -3-t-butylurea,

3 ['4- m-trifluoromethylbenzyloxy phenyl]-1,1-dimethylurea,

3- [4-(diphenylmethoxy) phenyl] -l,1-dimethylurea,

3-{4- [a-(p-chlorophenyl -a-phenylmethylthio] -phenyl}- 1,1-dimethylurea,

3-{3- 0t-( p-methylphenyl -a-phenylmethylsulfonyl] phenyl}-1-t-butylurea, etc.

Other suitable phenylurea compounds, too numerous to mention, will be obvious from reference to Formula II above. They may be readily ascertained by substituting one substituent or position of substitution for those specifically illustrated above.

HERBICIDAL COMPOSITIONS AND METHODS The substituted phenylurea compounds of this invention exhibit a broad range of contact, postemergence herbicidal activity as well as preemergence activity. They may be formulated as solids or liquids and directly applied to the foliage of the growing plants or incorporated in the soil or sand in which the plants are growing. Field application can be by such conventional techniques, as with powder dusters, boom and hand sprayers, spray dusters, addition to irrigation water and the like.

Generally, the phytotoxicants are initially formulated as concentrated compositions, comprising the active ingredient and a solid or liquid adjuvant. The adjuvant serves as a formulation aid or conditioning agent, permitting the concentrates to be further mixed with a suitable solid or liquid carrier, in a form which enables prompt assimilation by plant systems.

Useful liquid adjuvants in which the toxicant is dissolved, suspended or distributed include, for example, the following organic solvents and mixtures thereof: hexane, benzene, toluene, acetone, cyclohexanone, methyl ethyl ketone, isopropanol, butanediol, methanol, xylene, dioxane, isopropyl ether, ethylene dichloride, tetrachloroethane, hydrogenated naphthalene, solvent naphtha, and

petroleum fractions, such as, kerosene.

Useful solid adjuvants in which the toxicant is adsorbed or dispersed on or in include, for example: natural clays, such as china clays, bentonites and attapulgites; other natural materials, such as, talc, pyrophyllite, quartz, diatomaceous earth, fullers earth, chalk, rock phosphate, kaolin kieselguhr volcanic ash, salt and sulfur; chemically modified materials, such as acid washed bentonite, precipitated calcium phosphate, precipitated calcium carbonate, calcined magnesia, and colloidal silica; and other solid materials such as powdered cork, powdered wood and powdered pecan or walnut shells. For maximum adsorption and ease of handling, these materials are used in finely divided form of particles which range in size from 20 to 40 mesh (Tyler) or finer.

Prior to field application, the solid and liquid concentrate compositions are generally diluted by the addition of solid or liquid carriers. Suitable solid carriers, with which the concentrate compositions are mixed or adsorbed on or in, include: the previously mentioned solid adjuvants; fertilizers, such as, ammonium nitrate, urea, superphosphate, compost, manure and humus; pesticides; other herbicides; sand and the like. Suitable liquid carriers with which the concentrate compositions are dissolved, suspended, emulsified or dispersed include, for example, water and the liquid adjuvants previously mentioned.

Where solid concentrates are employed with liquid carriers they are advantageously employed in the form of powders made wettable by the addition of from about 1% to about 5% by weight of a dispersant, such as, a sodium salt of a high molecular weight carboxylic or sulfonic acid and about 1% to about 5% by weight of a wetting agent, such as, sodium oleylisethionate, lauryltrimethylammonium chloride, sodium lignin sulfate, etc., to a composition comprising about 25% to 90%, by weight, of the active compound and about 8 to about 9 73% by weight of the inert, finely divided solid. Three representative formulations are presented in Table I. v

10 EXAMPLE 1 Preparation of 3 p- (p-chlorobenzyloxy phenyl] 1, l-dimethylurea TABLE I ClQ-orh-QQmn U: Formu- Cl- N(CH3)3 latlon Weight No Ingredients percent 1 ign-(befntyloxy)phenyl]-1,1-dimethylurea 8. l1 1 e a Na iith lene sulfonic acid condensate 2 To a solution of p(chlorobenzyloxy)amlrne (3.5 g., Sodmm N-methvlINsleovlwumte 2 0.015 mole) in dry dimethylformamide (DMF) 80 ml.) II S-PI-(benaylsulfinyl)phenyl]-1,1-dimethylurea. so and dry triethylamine (3 ml.) was added dropwise with 323553 1; stirring an excess of dimethylcarbamoyl chloride (2.5 gm., 2 0.024 mole). The solution was set aside for 24 hours and then poured onto ice-Water (250 g.). The desired rod- 111 1-[p-(benzylsulfonyl)phenyl-3-methylurea. 75 p Diatomaceous earth 20 pct, 3-[p (p-chlorobenzyloxy)phenyl]-1,1-dimethy1urea, gfifigfiggfi gggfigif ggl392232)??? 3 1n the form of a white crystalline precipitate was rel A 108 A C C moved by filtration and purified by recrystallization from fggr N a iggg g a benzene-n-hexane mixture to give colorless needles Igepon A, Antara Chemicals Corporation. weighing 2.3 g. (49%) and having a m.p. of 149.5"-

150 C. Analysin Calcd. for C H N O CI: C, 63.05; H, 5.58;

Dusts are usually prepared by grinding together from N, 9 19; C1 1193, F und; C, 62.71; H, 5.66; N, 9.19; about 1% to about by welght of the active in- 01,1156 gredient with a solid adjuvant and solid carrier. In pre- EXAMPLES paring dust concentrates the active ingredient is usually 25 added in from about 25% to about 90% concentrations. The urea compounds Set forth Table In below were E prepared by the general procedure of Example 1, submulsifiable concentrates can be prepared by dissolving strtutrng the indicated base-solvent mixture and the apthe active ingredient (about 25% to about 75% by propriate aniline and carbamoyl chloride compounds for we1ght) in an organic solvent, such as, acetone, methylthe PChlorobenz 10X aniline and dimeth lcarb 1 isobutylketone, cyclohexanone, xylene or toluene and an y y amoy chloride used therein. emuls1fier (about 1% to 10% by weight), such as, for example, a non-ionic-anionic blend containing calcium EXAMPLE 9 dodecylbenzene sulfonate, such as Toximul R-S by Ninol Prepa 0f -(benzyloxy)phenyl]-3-methylurea Laboratories, Inc. and optionally a surfactant (about 1% CHQNCO to about 5%), such as, sodium lignin sulfonate. A representative formulation is presented in Table II. 1\IIH TABLE II Formw NHOONHCHa lation Weight To S-benzyloxyaniline (4 g., 0.02 mole), in dry ether Ingredients percent (100 ml.) and triethylamine (1 drop) was added methyl 1v iilp-lflilenzylthio)phenyl]-1,1-dirnethylurea isocyanate (2 g., 0.035 mole) at 10 with stirring. The

11 1'1 v v q n gg g $1,9 5; Xi mm S (equal 10 mixture was set aside at 25 C. for 20 hours. The desired product, l-[3-(benzyloxy)phenyl[3-methylurea, 1n the form of a crystalline precipitate, was removed from solution by filtration and dried. The crystalline product was tallized from benzene to ive 3.3 (66% theoreti- In general, postemergence control of undesirable plant recry? g 2 species is achieved by field applications in which the accal i punfiedf1'[iugenzz'loxwPhenynaqnethyl tive ingredient is applied in from about 0.5 ounce to i? F P a a 15 1 about 25 pounds per acre. The preferred range is from N '5 g 3 S g Q 70-29, about /2 ounce to about 4 pounds per acre. Preemergence 7 control is generally achieved by applications to the soil LES 10-13 of from about 1 to about 25 pounds of the active in- The urea compounds set forth in Table IV below were gredient per acre. prepared by the general procedure of Example 9, sub- The following examples illustrate the present invention stituting the indicated base-solvent mixture and apbut are not to be taken as limitative thereof. All parts and propriate aniline and isocyanate compounds for the 3- percentages are by weight unless otherwise indicated. benzyloxyaniline and methylisocyanate used therein.

. TABLE III I I I I Analysis (percent) Calculated Found Recrystal- Yield, Ex. Compound Solvent lized from- M.P., 0. percent 0 01 H N S 0 Cl H N S 2 3-[m-(benzyl0xy)phenyl1- DMF-pyr- Benzene 127. 5128.5 17 71.09 6.71 10.36 71.59 6.9 10.04

1,1-dimethylurea. idine. 3 3-[p-(benzyloxy)pheny1ldo .110 159. 5-160 53 71.1 6.7 10.36 71.1 6.2 9.89

1,1-dimethylurea. I 4 3-[p-(benzylthio)phenyl]- d0. Benzene- 144.5-145 67.1 6.3 9 8 11.2 67 1 6.2 9.8 11.2

1,1- 'methylurea. gycloexane. 5 3-l3-chloro-4 (p-ehloro- DMF-tri- Benzene..- 184-185 33 56.7 4.8 8.3 56.7 4.7 7.9

benzy10xy)pheny1]- ethyl- 1,1-dimethylurea. amine. 6 3-[4-(benzyloxy)3-chlorod0 Benzene- 116-117.5 34 63.1 11.9 5.6 9.2 63 5 11.8 5 6 8.8

phenyl]-1,1-dimethylhexane. 11 7 3-[4 g-methylbenzyl0xy)- ..do Benzene..." 144144.5 56 64.0 11.1 6.0 8.8 64.1 11 3 6.0 8.4

3-ehlorophenyl]-1,1- dimethylurea. 8 1-[4-(p-methylbenzyloxy) do do 1495-1505 23 71.8 7.1 9.9 71.6 7.4 10.0

phenyl]-3,3-dirnethylurea.

TABLE IV Analysis (percent) Solvcnt- Calculated Found base Recrystal- Yield, Ex. Compound mixture lized irom- M.P., C. percent Cl H N S C Cl II N S 10. l-[p-(benzylthio)phenyl]- Ethor-tri- Benzene 145-1455 60 66.2 5.9 10.3 11.8 66.2 5.9 10.2 11.6

3-mothylurea. ethylamine. 11.-. 1-[4(p-cholorobenzyloxy)- Ether- Benzene- 205-206 80 62.0 12.2 5.2 9.6 62.0 10.4 5.5 9.4

pl1enyl1-3-methylurea. pyridine. methanol. 12 l-[3-chloro-4-(p-chloro- Ether- Ethylaco- 1895-1905 35 55.4 4.3 8 6 55.5 4 3 8.6

benzyloxy)phenyl]-3- benzenetate-ninethylurea. pyridino. hexane; 13.. .1-[3-ch1or0-4-(p-methyl- Acetone- Acetonc- 214-215 63 65.80 10.24 6.64 8.08 65.84 10.36 8.81 7.99

benzyloxy)phenyl]-3-tpyridine. benzene.

butylurea.

EXAMPLE 14 r was added to a soluti n Preparation of 3-[p-(benzylsulfonyl)phenyl]-1,1- o of 3 (m Ifydroxyphanyl) 1,1(11

dimethylurea 20 methylurea (3.6 g., 0.02 mole) 1n anhydrous acetone 0 (100 ml.) and the resulting mixture was heated with x1 lzing Agent Q-CHT-S NHCON(CH3)2 @om-s OFQ-NHOO OH A chloroform (50 ml.) solution of 3-[p-(benzylthio)- phenyl]-1,1-dimethylurea (1.5 g., 0.005 mole) was cooled to C. and 85% aqueous solution of m-chloroperbenzoic acid (2 g., 0.01 mole) was added dropwise stirring. After the addition, the solution was set aside at 22 C. for 1 hour and hours at 10 C. The solution was washed successively with 10% aqueous sodium carbonate and water. The washed solution was dried over anhydrous magnesium sulfate, filtered and then distilled to remove the solvent leaving a solid having a m.p. of 162-163.S C. The solid was then purified by recrystallizing from an ethyl acetate-hexane (8:1) mixture to produce a white crystalline solid having a m p. of 183.5184.5 C., weighing 1.1 g. (33% theoretical yield).

Analysis.-Calcd. for C H N SO C, 60.4; H, 5.7; N, 8.8; S, 10.1. Found: C, 60.4; H, 5.6; N, 8.9; S, 10.0.

EXAMPLES 15-16 The urea compounds set forth in Table V below were prepared by the general procedure of Example 14, substituting the appropriate benzylthio compound for the 3- [p-(benzylthio)-phenyl]-1,1-dimethylurea used therein.

stirring under reflux for a period of about 30 minutes. Then p-cyanobenzyl bromide (4 g., 0.02 mole) in anhydrous acetone ml.) was added and the reflux was continued for 3 days. Absolute ethanol ml.) was then added and the reflux was continued for 1 day. The resulting mixture was poured onto an ice cold, 10% aueous solution of sodium carbonate and then extracted with benzene.

The reaction mixture was separated by chromatography on a silica gel column. The unreacted p-cyanobenzyl bromide was first eluted from the column with benzene. The desired product, 3-[3-(p-cyanobenzyloxy)phenyl]- 1,1-dimethylurea was then eluted from the column with a mixture of methylene chloride and acetone (9:1). The solvent was removed by evaporation, leaving 1.8 g. (30% theoretical yield). Purification was effected by recrystallization from benzene producing a crystalline product having a m.p. of l54155 C. and the following elemental analysis:

Calcd. for C H N O C, 69.13; H, 5.8; N, 14.23. Found: C, 69.30; H, 5.87; N, 14.13.

EXAMPLES 18-19 The urea compounds set forth in Table VI below were prepared by the general procedure of Example 17, sub- TABLEV Analysis (percent) Calculated Found Yield, Ex. Compound Recrystallized from-- M.P.,C. percent 0 H N S C H N S 15. 3-ga-(begzylsulfinyl)phenyl1-1,1- Ethylacetatebenzene 131-137 30 63.6 6.0 9.3 10.6 63.6 5.8 8.6 9.9

imet y urea. 16 l-fp-(benzylsulfonyl)phenyl1-3-methylurea Chloroform 178.5179.5 90 59.2 5.3 9.2 10.5 57.1 5.3 8.8 10.5

hemihydrate.

EXAMPLE 17 Preparation of 'Q'W stituting the appropriate hydroxy and benzyl bromide dlmethylulea compounds for the 3-(m-hydroxyphenyl)-1,l-dimethyl- Anhydrous potassium carbonate (2.8 g., 0.02 mole) 65 urea and p-cyanobenzyl bromide used therein.

TABLE VI Analysis (percent) Calculated Found Yield, Ex. Compound M.P.,C. percent; C Cl H N C Cl H N 18.... 3[3-(pehorobenzy!oxy)-phenyl]-1,1-dimethylurea 14 E 16 63.05 11.05 5.58 63.25 11.25 5.55 19.... 3-[3-(p-nitrobenzyioxy)-phenyl]-l.lnirnethylurea 144-145 16 60.94 5.43 13.33 61.16 5.31 13.28

1 7 EXAMPLE 39 Preemergence Herbicidal Activity in Sand The preemergence herbicidal activity of the compounds of Formula I is evident from the following greenhouse procedures in which seeds of Morning-Glory (Ipomoea purpurea) and Barnyard grass (Echinochloa crusgalli) were treated with representative compounds. The seeds were separately sown in 3.5 inch wax paper cups containing 335 grams of quartz sand. The seeds were placed approximately inches below the surface of the sand and sufficient Hoaglands nutrient was added in sutficient quantity to produce about 17% moisture by weight. The herbicidal compounds were added by pipetting 2 ml. of an acetone/water (50/50, by volume) solution onto the surface of the sand. For purposes of comparison 3-[p-(p'-chlorophenoxy) phenyl]-1,1dimethylurea, a commercial herbicide in the form of a 50% wettable powder formulation, was also applied in 2 ml. of water. In each case, quantities of the herbicidally active compound sufiicient to establish a rate of application equivalent to A3, A, 1 and 4 lb./ acre were employed. The treated cups were placed in a greenhouse for a period of about 3 weeks. Each day suflicient Hoagland nutrient solution was added to maintain the moisture level at 17%. Thereafter, the cups were removed from the greenhouse and the plants severed at the surface of the sand. The plants were immediately weighed and the rate of applicationrequired to produce 90% inhibition of growth was determined with the aid of a weight of a control plant, by plotting the percent of control achieved against the rate of application employed on log probability graph paper. The required rates of application are set forth below in Table IX.

18 What is claimed is: 1. A compound of the formula:

' NHCON(CH )a Q-CHz-Y I wherein Z is H or Cl, W is H or Cl, Y is S, 0, S0 or SO;

' and the substituents W and Y are attached at the 3 and 4 References Cited FOREIGN PATENTS 6906048 10/ 1969 Netherlands 260553 A 1,918,113 11/1969 Germany 260-553 A 2,006,525 12/ 1969' France 260-553 A 1,269,407 7/ 1961 France 260553 A OTHER REFERENCES Wagner et al.: Ann., vol. 675, p. 189-99 (1964).

BERNARD HELFIN, Primary Examiner M. W. GLYNN, Assistant Examiner US. Cl. X.-R.

260-453 A, 453 PH, 465 B, 465 E, 471 A, 518, 575;

' UNITED STATES PATENT OFFICE CERTIFICATE 0F CORRECTION Patent No. 3,819,697 Dated June 25, 1974 Inventor-(s) BARRINGTON CROSS It is certified that error appears in the above-identified patent and that said'Letters Patent are hereby correcte as shown below:

Claim 1, Column 18, delete the underlining from the first formula.

Claim 1, (Iol u mn 18, delete the entire second formula and brackets.

signed a'nd-sealed this 15th day of October 1974,

(SEAL) Attest:

MCCOY M. GIBSON JR. c. MARSHALL DANN Attesting Officer Commissioner of Patents USCOMM-DC GOING-P69 h u.s. sovzmmzm' rmu'rmo ornc: Ion o-sas-au F ORM PO-IOSO (10-69) 

